Reactive dyestuffs having a dithiocarbamyl-substituted triazine ring substituent



United States Patent REACTIVE DYESTUFFS HAVING A DETHIQCAR-BAMYLSUBSTITUTED TRIAZEJE RE IG SUE- STITUENT Frank Hall and Ian DurhamRattee, Manchester, England, assignors to Imperial Chemical IndustriesLimited, London, England, a corporation or Great Britain No Drawing.Filed Dec. 19, 1962, Ser. No. 245,650

Claims priority, application Great Britain, Mar. 11, 1959, 8,36G/S9; May21, 1959, 17,394/d; July 2, 1959,

wherein K represents the radical of a dyestuil selected from the classconsisting of azo, anthraquinone, nitro and phthalocyanine dyestufisradicals.

R represents a number selected from the class consisting of hydrogen andlower alkyl;

12 is a positive integer not exceeding 2;

Q is a member selected from the class consisting of chlorine, bromine,lower alkyl, phenyl, lower alkoxy, sulphonic acid, phenoxy, amino, loweralkylamino, hydroxy lower alkylamino, phenylamino, sulphophenylamino,carboxyphenylamino, N-phenyl-N-lower alkylamino, N-sulphophenyl N loweralkylamino, carboxysulphophenylamino, N-(carboxy sulphophenyl)-N-loweralkylamino, N-carboxyphenyl-N lower alkylamino, disulphophenylamino,N-disulphophenyl-N-lower alkylamino, cyclohexylamiuo, morpholino,piperidyl and and Z and Z are independently selected from the classconsisting of lower alkyl, phenyl lower alkyl, cyclohexyi and phenyl,and taken together Z and Z" form with the nitrogen atom N a heterocyclicring selected from the class consisting of piperidyl and morpholino.

' As examples of the lower alkyl radicals represented by each of R and Qthere may be mentioned alkyl radicals containing from 1 to 4 carbonatoms, in particular the methyl radical.

As examples of the lower alkoxy radicals represented by Q there may bementioned alkoxy radicals containing from 1 to 4 carbon atoms, inparticular the methoxy radical.

As examples of the lower alkylamino groups represented by Q there may bementioned N-(lower alky1)- amino and N:N-di(lower alkyl)amino groups,wherein lower alkyl represents an alkyl radical of from 1 to 4 carbonatoms, and as examples of such groups there may be mentionedmethylamino, ethylamino, propylamino, dimethylamino, diethylamino,dipropylamino, dibutylamino and N-methyl-N-ethylamino groups. Asexamples of the 3,136,979 Patented June 1, 1965 hydroxy lower alkylaminogroups represented by Q there may be mentioned N-(hydroxy loweralkyDamino and NzN-di-(hydroxy lower alkyl)amino groups such as N-(B-hydroxyethyl)amino and N:N-di(B-hydroxyethyl)amino groups.

As examples of the sulphophenylamino, carboxyphenylamino,disulphophenylamino and carboxysulphophenylamino groups represented by Qthere may be mentioned 2-, 3- or 4-sulphophenylamino, 2 3- or4-carboxyphenylamino, 225-, 3:5- or 2:4-disulphophenylamino and 4- orS-sulpho-2-carboxyphenylamino groups.

As examples of the N-phenyl-N-lower alkylamino, N- sulphophenyl-N-loweralkylamino, N-carboxyphenyl-N- lower alkylamino,N-disulphophenyl-N-lower alkylamino and N (carboxysulphophenyl) N- loweralkylamino groups represented by Q there may be mentioned N-phenyl-N-rnethylamino, N-phenyl-N-ethylamino, N-phenyl-N-n-propylamino,N-(2-, 3- or 4-sulphophenyD-N- methylarnino, N-(Z, 3, or4-carboxyphenyl)-N-methylamino, N-(2:5-, 3:5- or2:4=disulphophenyl)-N-methylamino and N-(4- or S-sulpho-Z-carboxyphenyDN-methlyamino groups.

As examples of the lower alkyl radicals representedby each of Z and Z"there may be mentioned methyl, ethyl,

propyl and butyl radicals; and as an example of a phenyl lower alkylradical represented by each of Z and Z" there may be mentioned thebenzyl radical.

Each of the groups of the formula:

present in the dyestulfs of the invention is attached to a carbon atompresent in the dyestuif radical represented by K. The said carbon atommay form part of an aryl ring, in particular a benzene or naphthalenering, present in K or may form part of an alkyl chain which is directlyor indirectly attached to an aryl ring present in K.

It is preferred that the dyestuli radical represented by K contains atleast one Water-solubilising group such as a carboxylic acid,sulphonamide, lower alkylsulphone, and, above all, a sulphonic acidgroup. If desired the dyestutl radical represented by K may also containa coordinately bound metal atom such as a coordinately bound copper,chromium or cobalt atom.

The dystufis of the invention may be obtained by reacting a dyestuifcompound of the formula: I

Formula II wherein K, R and n have the meanings stated, T represents achlorine or a bromine atom and Q represents chlorine, bromine, loweralkyl, phenyl, lower alkoxy, sulphonic acid, phenoxy, amino, loweralkylamino, hydroxy lower alkylamino, phenylamino, sulphophenylamino,carboxylamino, Nph-enyl-N-lower alkylamino, N-sulphophenyl- N-loweralkylamino, carboxysulphophenylamino, N-(carboxysulphophenyl)-N-loweralkylamino, N-carboxyphenyl-N-lower alkylamino, disulphophenylamino,N-disulphophenyl-N-lower alkylamino, cyclohexylamino, morpholino orpiperidyl, with a sulphur compound of the formula:

s z D-S.i l.N

Formula III wherein Z or Z" have the meanings stated above, and Drepresents a'metal atom, which is preferably an alkali metal atom suchas sodium or potassium.

This reaction may be conveniently brought about by adding a solution ofthe dyestufl compound of Formula II in water or in an organic liquid,which is preferably a Water-soluble organic liquid such as acetone, orin a mix-. ture of water and a water-soluble organic liquid, to anaqueous solution of the sulphur compound of Formula III, stirring themixture, preferably at a temperature below 50 C., for example at atemperature between 20 C. and 30 C., if necessary adding sodiumcarbonate to maintain the pH of the mixture between and 10, filteringoff the dyestuif which is precipitated. If necessary water and/ orsodium chloride, can be added to ensure complete precipitation of allthe dyestuif.

WhenT and Q each represent chlorine or bromine atoms then it is possibleby suitable choic of the reaction conditions to react one or both of thechlorine or bromine atoms with the sulphur compound. In general it isfound As example of such 1:3:5-triazines there may be mentioned cyanuricchloride, cyanuric bromide, 2-methyl- 4: 6-dichloro-1 :3 S-triazine,2-methoxy-4: 6-dichloro-1 :3: 5 -triazine, .2-phenyl-4: 6-dichloro-1 :3S-triazine, 2-phenoxy-4:6-dichloro-1 :3 :S-triazine, Z-methylamino 4:6-dichloro-lz3z5-triazine, 2-ethylamino-4:-6-dichloro 113:5- triazine,2-N N-diethylamino-4: 6-dichloro-1 :3 S-triazine, 2-phenylamino-4:6-dichloro h 1:3 :5 triazine, 2 phenylcompounds isdirectly attached'to a'carbon atom of an .aryl residue present in thedyestuif compound or each of that by carrying out the reaction at atemperature between 7 0- and 10 C., only one of the said chlorine orbromine atoms reacts with the sulphur compound, whereas at highertemperatures both of the chlorine or bromine atoms react with thesulphur compoundl The sulphur compounds of Formula III may themselves beobtained by reaction a secondary amine of the formula: 1 I

wherein Z" and 2 have the meanings stated above, with carbon disulphidein Water in the presence of an alkali metal hydroxide, at a temperaturebetween0 and C. and at pH above 12, adding sodium chloride, filteringoff the precipitated compound, washing it with toluene and drying it atatemperature below 45 C.

As examples of the sulphur compounds of Formula III there may bementioned sodium diethyldithiocarbamate, sodiumpentamethylenedithiocarbamate, sodium dimethyldithiocarbamate, potassiumdipropyldithiocarba mate, sodium N-methyl-N-propyldithiocarbamate, sodium N-methyl-N-ethyldithiocarbamate, sodium diphenyldithiocarbamate,sodium N-phenyl-N-methyldithiocarbamate, sodiumdicyclohexyldithiocarbamate, potassium di-n-butyldithiocanbamate, sodium4-morpholinodithiotar bamate, sodium"diiso-butyldithiocarbarnate,'sodium N-i methyl-N-cyclohexyldithiocarbamate and sodiumN-benzyl-N-ethyldithiocarbamate. Such compounds may if desired be usedin the form of their hydrates with water.

The dyestufi compounds of Formula 11 may themselves be obtained byreacting a dyestufi compound of the formula K(NHR),,, wherein K, R and nhave the meanings stated above, with a 1:3:5-triazine of the formula:'.V

. Formula IV V wherein T and Q' have the meanings stated, one molecuaeach --NHR group present in the dyestutf compound.

1-ar proportion of the said 1:3:5-triazine being used'for the -NHRgroups is attachedtoa carbon atom of an alkyl radical which is directlyattached to an aryl residue present in the dyestulf compound or which isattached to an aryl residue through a bridgingiatom or group. As ,7

tained by any of the methods known for preparing dyestufis containingamino or substituted amino groups. Thus, for example, an azo compoundcontaining one or two NHR groups, where R has the meaning stated above,may be obtained by coupling a diazotised amine with a couplingcomponent, the amine and coupling component being'so chosen that theresulting azo dyestuff contains one or two NHR groups, or contains oneor two groups, for example one or two -NR.COCH groups, which are readilyconvertible to --NHR groups. V

As' examples of the said dyestutf compounds of'the formula K{-NHR) ashereinbefore defined, there may be mentioned the dyestufi compounds ofthe'follo'wing classes without, however, limiting the classes to thosespecifically described.

(l) Dyestufi compounds of the formula:

2 NHR V a 6 S 0 N wherein D repre sents a phenyl or a 'naphthyl radicalwhich may contain further substituents, and the --NHR group ispreferably attached to the 6- or 7-position of the naphthalene nucleus.r V V Particularly valuable dyestuff compounds are those wherein'D'represents a phenyl radical which contains an SO H group'in orthoposition to the azo link and, if desired, the phenyl radical maybe'further substituted by, for example, halogen atoms such as chlorine,alkyl radicals such as methyl, acylaminogroups such as acetylamino,alkoxy radicals such as methoxy, and sulphonic acid groups, and thosewherein D represents'a. 1-sulpho-2- naphthyl radical.

Also in this class are'the dyestuff compounds wherein D represents aradical of the'azobenzene, azonaphthalene V orphenylazonaphthaleneseries.

I (2) Dyestufi compounds of the formulaz I V ust 1 11111 s ulpho-Z-naphthyl rfadical.

(3) Dyestufi compounds of the formula:

wherein D stands for a phenyl or naphthyl radical which may containfurther substituents and is preferably a disulphonaphthylene radical,and the benzene nucleus may contain further substituents such as halogenatoms, alkyl radicals, alkoxy radicals and acylamino groups.

(4) Dyestuff compounds of the formula:

wherein D represents an arylene radical which may contain furthersubstituents and V represents the residue of a naphthol sulphonic acidwhich may contain further substituents, or the residue of aketomethylene compound such as the residue of an acetoacetarylide or aS-pyrazolone. D preferably represents a sulphophenylcne radical.

(5 Dyestuif compounds of the formula:

wherein D represents an aryl radical, preferably a phenyl or naphthylradical, which may contain further substituents such as a sulphonic acidgroup and/ or an azo group and K represents the residue of a couplingcomponent which contains a CO.CH group, such as an acetoacetarylide or a5-pyrazolone.

(6) The metal complexes, in particular the copper, chromium or cobaltcomplexes, of the dyestuff compounds of classes 1, 2, 4 and 5 whichcontain a metallisable group, in particular a hydroxy, carboxy or loweralkoxy group, attached to D D or D, in ortho position to the azo group.

(7) Dyestuff compounds of the formula:

i) I1TH-YNHR wherein the anthraquinone nucleus may contain an additionalsulphonic acid group in the 5-, 6-, 7- or 8-p0sition and Y represents abridging group which is preferably a phenylene radical which may containfurther substituents such as a sulphonic acid group.

(8) Dyestuif compounds of the formula:

(S OzNH-Y-NHR) 111 wherein 'Pc represents a phthalocyanine radical andis preferably a copper phthalocyanine radical, w represents -()H and/orNH Y represents a bridging group, preferably an aliphatic,cycloaliphatic or aromatic bridging group, p and In each represent 1, 2or 3 and may be the same or diiferent provided that p+m is not greaterthan 4.

As specific examples of the said dyestuii? compounds of the formula:IKHJI IRL. there may be mentioned:

6-amino-l-hydroxy-Z-(2'-sulphophenylazo)napthalene- S-sulphonic acid,

6-methylaminol -hydroxy-2- (4-acetylamino-2-su1phophenylazo)naphthalene-3-sulphonic acid,

S-aminol-hydroxy-Z- (2.-sulphophenylazo -naphthalcue-3 G-disulphonicacid,

8-amino-l-hydroxy-Z-(4'-chloro-2-su1phophenylazo)- naphthalene-3:S-disulphonic acid,

7-amino-2- (2' S-disulphophenylazo -1-hydroxy-naphthalene-El-sulphonicacid,

7-methylamino-2-(2-sulphophenylazo)-l--hydroxynaphthalene-S-sulphonicacid,

7-met-hylamino-2-(4'-methoxy-2-sulphophenylazo)-1-hydroxynaiphthalene-sulphonic acid,

8-( 3 '-aminobenzoylamino) -1-hydroXy-2(2-su1phophenylazo )naphthalene-36-disulphonic acid, 8-aminol-hydroxy-Z :2'-azonaphthalene-1' 3 :56-tetrasulphonic acid,

S-amiuo-l-hydroxy-Z: 2'-azonaphthalene-1 3 :5 '-trisulphonic acid,

G-aminol-hydroxy-Z 2'-azonapl1thalene-1' 3 5-trisulphonic acid,

7-aminoal -hydroXy-2:Z-azonaphthalene-d :3 -disulphonic acid,

8-amino-1-hydroxy-2- (4'-hydroxy-3 '-carboxyphenylazo)naphthalene-3fi-disulphonic acid,

G-aminoi-hydroxy-Z- (4'-hydroxy-3'-carboxyphenylazo)naphthalene-3:S-disulphonic acid.

8-amino-1-hydroxy-2- [4'- (2-sulphophenyl-az-o -2-meth- :oXy--methylpheny1azo] naphthalene-3 o-disulphonic acid,

8-amino-1-hydroXy-2- [4'- 4"-methoxyphenylazo -2- carboXy-phenylazo]naphthalene-3 6-disulphonic acid,

S-amino-l-hydroxy-Z- [4-( -hydroXy-3 6"-disulpho- 1"-naphthylazo -2-carboxyphenylazo] naphthalene- 3 :6-disulphonic acid,

6-amino-1-hydroxy-2- [4- (2"-sulphophenylazo) -2- metho xy-S'-methylphenylazo] naphthalene-3 :S-disulphonic acid.

2- (4'-amino-2'-methylphenylazo naphthalene-4: 8-disulphonic acid,

2- (4'-amino-2"-acetylaminophenylazo naphthalene-S 7- disulphonic acid,

4-nitro-4'- (4"-methylaminophenylazo) stilbene-2: 2'-

disuiphonic acid,

4nitro-4'-(4"-arnino-2-methyl-5-methoxyphenylazo)stilbeneQzW-disulphonic acid,

4-amino-4'- 4"-methyloxypheny1azo stilb ene-Z 2-disulphonic acid,

4-amino-2-methylazobenzene-Z' S-disulphonic acid.

1- (3 '-arninophenyl) -3-methyl-4-(2' 5 '-disulphophenylazo-5-pyrazolone,

1-( 3 -amin0phenyl) -3-carb oxy-4- 2-carb oXy-4'-su1phophenylazo)-5-py1'azolone,

4-amino-4- [3 "-methyl-4- (2"' fi -disulphophenylazo 1"-pyrazol-5"-onyl]stilbene-Z 2-disulphonic acid,

The copper complex of 8-amino-1-hydroXy-2-(2'-hydroxy-5'-sulphophenylazo)naphthalene-3 :6-disul phonic acid,

The copper complex of 6-amino-1-hydroXy-2-(2'-hydroxy-5'-sulphophenylazo)naphthalene-B-sulphonic acid,

The 1 :2-'chromium complex of The copper complex of6-amino-1-hydroxy-2-(2-hydr0xy- -sulphophenylazo naphthalene-35,-disulphonic acid,

The copper complex of 8-amino-l-hydroxy-2-(2'-hydroxy- The coppercomplex of 8-amino-1-hydroxy-2-[4' (2"-sulphophenylazo -2'-methoxy-5'-methylphenylazo] naphthalene-3:6-disulphonic acid;

The copper-complex of 6-amino-1-hydroxy-2[4'-(2":5"-

disulphophenylazo) -2',-met-hoxy- 5 -methy-lpheny-lazo]naphthalene-3:S-disulphonic acid, 7 l

The copper complex of 1-(3'-amino-4-sulphophenyl)-3- methyl-4- [4"- (2"5"-disulphophenylazo -2"-me-' thoxy-5"-methylphenylazo]-5-pyrazolone,

The copper complex of 7-(4'amino-3-sulphoanilino)-1- hydroxy-Z- [4"-(2"' 5"-disulphophenylazo -2"-meth-oXy-S met-hylphenyl azo]naphthalene-3-sulplronic acid, i

The copper complex of 6-(4'-amino-3-sulphoanilino)-1-hydroxy-2-(2-carboxyphenylazo)-rraphthaIene-B- sulphonic acid,

The 1:2-chromium complex "of 7-amino-6'-nitro-1:2'-di hydroxy-Z:1-azonaphthalene-3' 4'-disulphonic acid,

The 1:2-chromium complex of 6-amino-1-hydroxy-2-(2'-carboxyphenylazo)naphthalene-3-sulphonic acid,

The 1:2-chromium complex of 8-amino-1-hydroxy-2-(4'- nitro-2'-hydroxyphenylazo) naphthalene-3 :6- disulphonic acid,

j The 1:2-cobalt complex of 6-(4'-amino-3{-sulphoanilino)-l-hydroxy-Z-(5"-chloro-2"-hydroxyphenylazo)naphthalene-3-sulphonic acid,1

1- 3.'-ami,n0-s4' ulphophenyl)-3-methy1-4-(2"-hydroxy-4"sulpho-1"-naphthylazo) -5-pyrazolone, The 1:2-chromium complex of7-(4'-sulphoanilino)-slhydroxy-2-(4"-amino-2-carboxyphenylazo)naphthalene-3-sulphonicacid, r p The 1:2-chromium complex of 1-(3'-aminophenyl)-3- methyl-4%"-nitro2"-carboxyphenylazo}S-pyraZ lone'. 1-amino-4- 3amino-4'*sulphoanilino anthraquinone- 2-sulphonic acid, I 5 V 1-amino-4-(4'-amino-3-sulphoanilino) anth'raquinone- 2:5-disulphonic acid, a 11-arnino-4- [4'- (4"-amino-3"-sulphophenyl anilinoanthraquinone-Z:S-disulphonic acid, 1-amino-4[4f-amino-2"-sulphophenylazo )anilino] anthraquinQne-ZfS-disulphonicacid, 1-amino-4- (4'-methylamino-3 '-su lpho anilino)anthraquinone-2sulplionic acids 3-(3-amino-4-sulphophenyl)sulphamylcopper phthalo cyanine-tri3-sulphonic acid, i

Di-4-(3-amino-4'-sulphophenyl)sulphamyl copperph'thalocyanine-di-4-sulphonic acid, 7 Copper phthalocyanine3-sulphon-N-(3'-amino-4-sulpho phenyl)amide 3-sulphonamide 3-sulphonicacid, Copper phthalocyanine 3-sulphon-N-(4'-amino-3-sulpho pheny1)amide3-sulphonamide 3-su1phonic acid.

- ocyanine-di-3-sulphonic acid, and V V 4-amino-2'-nitr0 diphenylamine 3:4'-disulpl1onic acid. 4 V

i Dyestufi compounds of Formula I, as hereinbeforende fined, which-canbe used 'to obtain the dyestuffs of the invention are described inBritish specifications Nos.

' 3-(3'-aminophenylsulphamyl)13-sulpharnyl-copper phthal 571,523,571,893, 571,942, 572,491, 572,833, 572,967 and 581,401, in Italianspecifications Nos. 577,309, 582,676, 584,124 and 594,999, and in UnitedStates specifications wNos. 2,258,977, 2,680,129, 2,860,128, 2,873,269,2,891,941 and 2,910,464. 7

Alternatively the new dyestulfs, as hereinbefore defined, can beobtained by reacting a dyestufi compound of the formula:K{NHR),,wherein.K, R and n have the meanings stated above, with a 1:3:S-triazine of the formula:

wherein T, Q, Z and Z have the meanings stated, one molecular proportionof the said 1:3:5-triazine being used for each NHR group present in thedyestufl compound.

This alternative method may be,conveniently' brought about by adding asolution of the said dyestutf compound in water or in awater-solubleorganic liquid or in a mix ture of water and a water-soluble organicliquid, to a solution or suspension of the said triaz'ine in waterand/or a water-miscible organic liquid, stirring the mixture, pref--er-ably at a temperature between 0 C. and 30 C.,'adding sodium carbonateto maintain the pH of the mixture between 5 and 10, filtering ofithedyestufi which is precipitated. If necessary water and/orsodium'chloride can be added'tojensure complete precipitation of allthe'dyestuif. The 1:3:5-triazines of Formula V'may themselvesbe obtainedby reacting a 1:3:5-triazine of FormulalV with a sulphur compound ofFormula 111.

Alternatively the dyestuffs wherein K represents the radical of an azodyestulf may be obtained by coupling a diazotised amine with a couplingcomponent, theamine and coupling component together containing one ortwo groups of Formula I. This may be conveniently brought about byadding sodium nitrite to a solution or suspension of the amine, whichmay be an aminoazo compound, in an aqueous solution of hydrochloric acidand adding the soobtained solution or suspension of the diazo compoundto a solution of the coupling component and isolating, by

wherein Q represents lower alkoxy,jsulphonic acid, phen oxy, amino,lower alkylamino, hydroxy'lower alkylamino, phenylamino,sulphophenylamino, carboxYphenylamino, N-phenyl-N-lower alkylamino,N-sulph-ophenyl-N-lower alkylamino, N-(carboxy-sulphophenyl)-N-lowera'lkylamino, N-carboxy-phenyl-N-lower alkylamino, disulphophen-,ylamino, N-disulphophenyl-N-lower alkyl-amino, cyc1o-' hexylamino,morpholino and piperidyl, may be obtained by reacting a dyestuff ashereinbefore defined wherein Q representschlorine or bromine, with acompound of the formula: 'P-p-G wherein P represents ahydrogen or ametal atom-and G represents lower. alkoxy, sulphonic acid, phenoxy,amino, lowersalkylamino, hydroxylower alkylamino, phenylamino,sulphophenylamino, carboxyphenyl amino, N-phenyl N lowersalk ylamino, Nsulphophen yl-N lower alkylamino, N (carboxysulphophenyl)- N- loweralkylamino, N-carboxyphenyl -'N lower alkyl amino, disulphophenylamino,N disulphophenyl N lower alkylamino, cyclohex'ylamino, morpholino and"and the new dyestuir', as hereinbefore defined, in water, or in awater-miscible organic liquid, or in a mixture of water and awater-miscible organic liquid, preferably at a temperature between and100 0., adding sodium carbonate to maintain the pH of the mixturebetween and 10, and filtering oir' the dyestufi which is precipitated.If necessary water and/ or sodium chloride can be added to ensurecomplete precipitation of all the dyestufl.

As examples of compounds of the formula: PG which may be used there maybe mentioned methanol, phenol, ammonia, methylamine, diethylarnine,aniline, metanilic acid, sodium sulphite, ,B-hydroxyethylamine,di(;3hydroxyethylarnine), cyclohexylamine, morpholinc, N-methylaniline,sulphanilic acid, aniline-2:4-, 2:5- or 3:5-disulphonic acid and 4- orS-sulphoanthranilic acid.

If desired the new dyestuffs, as hereinbefore defined, can be isolatedfrom the medium in which they have been formed and/or subsequently driedin the presence of a buffering agent. As examples of buit'ering agentswhich can be used for this purpose there may be mentioned bufferingagents derived from phosphates such as sodium dihydrogen phosphate anddisodium hydrogen phosphate, citrates such as sodium citrate, boratesand dialltylmetauilic acid such as sodium diethylmetanilate, which ispreferably used in conjunction with sodium hydrogen sulphate.

Preferred classes of dyestuds of the invention are the dyestuffs whichare represented by the formulae In these preferred classes it is furtherpreferred that K is a radical of a dyestuii selected from the classconsisting of azo, antbraquinone and phthalocyanine dyestulf radicalswhich, preferably, contains at least one water-solubilising groupselected from the class consisting of sulphonic acid and carboxylic acidgroups, that R is a hydrogen atom, and that Z and Z" each representlower allryl radicals, in particular ethyl radicals.

The new dyestuffs, as hereinbefore defined, are valuable for colouringnatural and artificial textile materials for example textile materialscomprising cotton, viscose rayon, regenerated cellulose, wool, silk,cellulose acetate, polyamides, polyacrylonitriie, modifiedpolyacrylonitrile and aromatic polyester fibres. For this purpose thedyestutls can be applied to the textile materials by dyeing, padding orprinting using printing pastes containing the conventional thickeningagents or oil-in-water emulsions or water-in-oil emulsions, whereby thetextile materials are coloured in bright shades possessing excellentfastness to light and to wet treatments such as washing. It is alsofound that the dyestuffs build-up well to give heavy depths of shade ontextile materials.

The dyestuffs of the invention have excellent stability to storage, thatis to say the dyestuffs undergo little or no loss in strength whenstored either at normal temperatures for example at 20 C., or atelevated temperatures, for example at 60 C.; and in this respect theyare superior to the corresponding known dyestuffs having lb chlorine orbromine atoms attached to the triazine ring instead of groups.

The new dyestufis which contain water-solubilising groups, for examplesulphonic acid and carboxylic acid groups, which render them soluble inwater are particularly valuable for colouring cellulose textilematerials. For this purpose the dyestuffs are preferably applied to thecellulose textile material in conjunction with a treatment with anacid-binding agent, for example sodium carbonate, sodium metasilica-te,trisodium phosphate or sodium hydroxide, which may be applied to thecellulose textile material before, during or after the application ofthe dyestuif. Alternatively when the dyed textile material is to besubsequently heated or steamed a substance such as sodium bicarbonate orsodium trichloroacetate, which on heating or steaming liberates anacid-binding agent, can be used.

For example the cellulose textile material can be coloured by treatingthe cellulose textile material with an aqueous solution or suspension ofthe acid-binding agent and then immersing the so-treated cellulosetextile material in a dyebath comprising a solution or dispersion of oneor more of the new dyestuffs, as hereinbefore defined, at a temperatureof between 0 and C., removing the dyed cellulose textile material fromthe dyebath and if desired subjecting the dyed cellulose textilematerial to a treatment in a hot aqueous solution of soap.

If desired the cellulose textile material which has been treated with anaqueous solution or suspension of the acid-binding agent may be passedbetween rollers to remove excess aqueous solution or suspension of theacidbinding agent and/ or dried before being treated with the aqueoussolution or dispersion of the said dyestuffs.

Alternatively the aqueous solution or dispersion of the dyestufi may beapplied by padding to the cellulose textile material which has beentreated with the acid-binding agent and the cellulose textile materialthen passed through rollers and subsequently subjected to the action ofheat or steam. Alternatively the cellulose textile material can bepadded with an aqueous solution or dispersion of one or more of the newdyestuffs, as hereinbefore defined, which also contains an acid-bindingagent, passing the so-treated cellulose textile material throughrollers, then if desired drying the cellulose textile material at asuitable temperature, for example 70 C., and then subjecting thecellulose textile material to the action of heat or steam. Alternativelythe cellulose textile material can be dyed by immersing it in a dyebathcomprising an aqueous solution or dispersion of the one or more of thesaid dyestuffs which also contains an acid-binding agent, at a suitabletemperature for example between 0 and 100 C., and thereafter removingthe cellulose textile material from the dyebath, if desired subjectingit to a treatment in a hot aqueous solution of soap and finally dryingthe dyed cellulose textile material. Alternatively the aqueous solutionor dispersion of one or more of the said dyestuffs can be applied to thecellulose textile material by a dyeing or a padding method and thecoloured cellulose textile material subsequently immersed in an aqueoussolution or suspension of the acidbinding agent, preferably at atemperature between 50 C. and 100 C., or alternatively the colouredcellulose textile material may be padded with an aqueous solution orsuspension of the acid-binding agent, the textile material dried andthen subjected to the action of heat or steam. Alternatively thecellulose textile material can be dyed by immersing it in a dyebathcomprising an aqueous solution or dispersion of one or more of the saiddyestuffs, preferably at a temperature between 20 1 1 and 100 C., and,after the textile material has'absorbed some or all of the dyestuffs,adding an acid-binding agent and proceeding with the dyeing at'the sameor a different temperature. 1

The concentration'of the acid-binding agent present in the aqueoussolution or suspension or in the aqueous dispersion of the dyestuffs isnot critical but it is preferred to use between 0.1% and of theacid-binding agent based on the total weight of the aqueous solution orsuspension. Ifdesired the aqueous solution or suspension of the acidbinding agent may also contain further substances, for exampleelectrolytes such as sodium chloride and sodium sulphate.

The aqueous solution or dispersion of the one or more of thesaiddyestuffs may also contain substances which are known to assist theapplication of dyestuffs to textile materials, for example sodiumchloride, sodium sulphate, urea, dispersing agents, surface activeagents, sodium alginate or-an emulsion of an organic liquid, forexample, trichloroethylene in water.

Alternatively the cellulose textile materials can be printed with aprinting paste containing one or more of the new dyestuffs of theinvention.

This may be conveniently brought about by applying a printing pastecontaining one or more of the said dyestuffs, to a cellulose textilematerial which has been impregnated with an acid-binding agent andthereafter subjecting the printed cellulose textile material to theaction of heat or steam. Alternatively a printing paste containing oneor more of the said dyestuffs and containing an acid-binding agent canbe applied to the cellulose textile material and the printed cellulosetextile material subsequently subjected to the action of heat or steam.Alternativelyfa printing paste containing one or more of the saiddyestuifs can be applied to the cellulose textile material which issubsequently immersed in a hot aqueous solution or suspension of theacid-binding agent or alternatively the printed textile. material isimpregnated with an aqueous solution or suspension of-theacidbindingagent and subsequently subjected to the action of heat or steam.

' After applying the printingpaste to the cellulose tex- V tile'materialthe printed textile material may, if desired, be dried, for example'atatemperature between 20 and 100 C., before the printed textile materialis subjected to the action of heat or steam.

The cellulose textile material may be printed with the printing paste byany of the commonly'known methods of applying printing pastes to textilematerials, for example by means' of roller printing, screen printing,block printing, spray printing or stencil printing. The printing pastesmay also contain the commonly used adjuvants,

for example urea, thickening agents, for example methyl cellulose,starch, locust bean gum, sodium alginate, waterin-oil emulsion,oil-in-water emulsion, surface active agents, sodium m-m'trobenzenesulphonate, and organic liquids, for example ethanol. p t

' At the conclusion of the dyeing and/or printing processes it ispreferred to subject the sic-coloured cellulose textile materials to a'soa-ping treatment, which may be carried out by immersing the colouredcellulose textile materials for a short time, for example minutes, in ahot aqueous solution of soap and/ or detergent, andsub sequently rinsingthe coloured cellulose textile material in water. before drying it. I

- Those newdyestufis which do not contain water-solubilising groups forexample'sulphonic acid, carboxylic acid, sulphonamide andacylsulphonamide groups are, in general, applied to textile materials inthe form of an aqueous dispersion which may beobtained by gravel millingthe dyestulf with water in the presence of a dissurface-active materialswith or without protective colloids such as dextrin, British gum andwater-soluble'proteins. If desired the aqueous paste of the dyestuffs soobtained may be dried to form a re-dispersible powder which may beconverted to a nonedusting powder by any of the processes known forforming'non-dusting powders,

The new dyestufis, as hereinbefore defined, can be applied tonitrogen-containing textile materials such as wool and polyamide textilematerials, from a mildly alkaline, neutral or acid dyebath. The dyeingprocess can be carried out at a constant or substantially constant pH,that is to say the pH of the dyebath remains constant or substantiallyconstant during the dyeing process, or if desired the pH of the dyebathcan'be altered at any stage of the dyeing process by the addition ofacids or acid salts or alkalis or alkalinesalts. For example dyeing maybe started at a dyebath pH of about 3.5 to 5.5 and raised during thedyeing process to about 6.5 to 7.5 or higher if desired. The dyebath mayalso contain substances which are commonly used in the dyeing ofnitrogen-containing textile materials. As examples of such substancesthere may be' mentioned ammonium acetate, sodium sulphate, ethyltartrate, non-ionic dispers ing a'gentssu-ch as condensates of. ethyleneoxide with amines, fatty alcohols or phenols, surface active cationicagents such as quaternary ammonium salts for example cetyltrimethylammonium bromide and cetyl pyridinium bromide and organicliquids such as n-butanol and benzyl alcohol; r .7

We are aware of British'specification No. 363,690

. which relates to a manufacture of triazine derivatives persing agent,for example the sodium salt of sulphoethylene oxide condensationproducts, soap and similar 'ment'with a saponifying or reducing agent.

containing sulphur, by causing a compound of the general formula: 7 r

in which X is a halogen atom or any desired residue and in which thereis still present at least one halogen atom capable of exchange, to reactwith one, two or three molecular proportions of a sulphur compound, inwhich at least one sulphur atom is united on the one hand to a metal andon the other hand to a residue capable of being split oif, and causingthe product thus obtained, so far as it still contains reactive halogenatoms, to react The invention is illustrated but not limited by thefol-' lowing examples in which the parts and percentages are by weight:7 l Example 1 A solution of 22 parts of sodium diethyldithiocarb amatetrihyd-rate in 50 parts of water is added with stirring to a solution of18 parts of the trisodium salt of 7-(2- sulphophenylazo)-1-(4":6"-dicl1loro 1":3":5" triazin 2"-ylamin-o)-8-naphthol-3:6-disulphonic acid (which may be obtained as described in Example 1 ofBritish specification No. 785,222): in 1000 parts of water and theresulting mixture is stirred for 3 hours at a temperature between 20?and.22 C. parts of potassium chloride V are then added an'dthe dyestuffwhich is precipitated is filtered off and dried at a temperature of 40C. On analysis the dyestulf isfound to contain 7 sulphur atom for eachmolecule of the dyestuff.

When applied to cellulose textile materials in con- 13 function with atreatment with an acid-binding agent the dyestufif yields red shadespossessing excellent fastness to washing.

Example 2 A solution of 22 pants of sodium diethyldithiocarbamatet-rihydrate in 100 parts of water is added with stirring to a solutionof 15.3 parts of the disodium salt of 2-[4'-(4": 6"-dichloro 1:3":5"triazin 2-ylamino)- 2-methylphenylazo]-naphthalene 4:8 disulphonic acid(which may be obtained as described in Example 1 of Britishspecification No. 774,925) in 1000 parts of Water. The mixture is thenstirred for 20 hours at a temperature of 20 C. 130 parts of sodiumchloride are then added and the precipitated dyestufi" is filtered oiland dried at 40 C. On analysis the dyestuff is found to contain 5.3atoms of sulphur for each molecule of the dyestuff.

When applied to cellulose textile materials in conjunction with atreatment with an acid-binding agent the dyestuff yields bright yellowshades possessing excellent fastness to washing.

Example 3 A solution of 34 parts of sodium diethyldithiocarbamatetrihydrate in 100 parts of water is added with stirring to a solution of29.3 parts of the trisodium salt of l-amino 4 [4'-(4":6"-dichloro 1":3:5niacin-2- ylamino)anilino] anthraquinone-2z3z5 trisulphonic acid (whichmay be obtained as described in Example 1 of British specification No.781,930) in a mixture of 650 parts of water and 50 parts of acetone. isthen stirred for 20 hours at a temperature of 20 C. and a aqueoussolution of hydrochloric acid is added until the pH of the mixture hasfallen to 7.5. 30 parts of sodium chloride are then added and thedyestufr which is precipitated is filtered oil, and dried at 40 C. Onanalysis the dyestull is found to contain 7 sulphur atoms for eachmolecule of dyestutl.

When applied to cellulose textile materials in conjunction with atreatment with an acid-binding agent the dyestutl yields bright blueshades possessing excellent fastness to Washing.

Example 4 In place of the 34 parts of sodium diethyldithiocarbamatetrihydrate used in Example 3 there are used 21 parts of sodiumdimethyldithiocarbamate. ()n analysis the dyestutf so obtained is foundto contain 6.7 sulphur atoms for each molecule of dyestuff.

When applied to cellulose textile materials in conjunction with atreatment with an acid-binding agent the dyestuif yields bright blueshades possessing excellent fastness to washing.

Example 5 A solution of 5.03 parts of sodium pentamethylenedithiocarbamate in 60 parts of water is added with stirring to asolution of 8.95 parts of the trisodiumsalt of 7-(2-sulphophenylazo) 14":6 dichloro 1:3":5" triazin-2-ylamino) 8 naphthol 3:6 disulphonic acid(which may be obtained as described in Example 1 of Britishspecification No. 785,222) in 250 parts of water and the resultingmixture is stirred for 2 hours at a temperature between and 22 C. andthen for 2 hours at a temperature between and C. 80 parts of potassiumchloride are then added and the dyestufi which is precipitated isfiltered oh and dried at a temperature of C. On analysis the dyetuff isfound to contain 7 sulphur atoms for each molecule of the dyestuff.

When applied to cellulose textile materials in conjunction with atreatment with an acid-binding agent the dyestuff yields red shadespossessing excellent fastness to washing.

Example 6 A solution of 5.03 parts of sodiumpentamethylenedithiocarbamate in parts of Water is added with stirringto ,a solution of 7. 64 parts of the disodium salt of The mixture amino)2' methylphenylazo] naphthalene 4:8 disulphonic acid (which may beobtained as described in Example 1 of British specification No. 774,925)in 500 parts of water. The mixture is then stirred for 10 hours at atemperature of 20 C. and then for 10 hours at .a temperature between 30C. and 35 C. 70 parts of sodium chloride are then added. and theprecipitated dyestulf is filitered oil and dried at 40 C.

When applied to cellulose textile materials in conjunction with atreatment with an acid-binding agent the dyestufi yields bright yellowshades possessing excellent fastness to washing.

Example 7 V A solution of 49.5 parts of sodium diethyldithiocarbamatet-rihydrate in 400 parts of Water is added during 15 minutes to asolution of 51.1 parts of the disodium salt of1-(4':6'-dichloro-l:3':5'-triaain-2'-ylamino)-8-naphthol-3,6-disulphonic acid in 1200 parts of Water, the temperature ofthe mixture being maintained between 20 C. and 25 C. during andsubsequent to the addition. A mixture of 8.58 parts of sodium hydrogenphosphate and 16.42 parts of potassium dihydrogen phosphate are thenadded and after 20 hours 400 parts of potassium chloride are added. Thedipotassium salt of 1-[4:6-bis (diethyldithiocarbamyl) 1':3:5' tr-iazin-2-ylamino]-8- naphthol-3:6disulphonic acid which is precipitated isfiltered off,'washed with ethanol and dried at 20 C.

To a solution of 19.2 parts of the dipotassium salt of 1 [4 6bis(diethyldithiooarbamyl) 1:3': 5 triazin-2'-ylamino]-8-naphthol-3:6-disulphonic acid in 200 parts of water, whichhas been previously cooled to a temperature between 5 C. and 10 C.,there is gradually added an aqueous solution obtained by diazotising4.88 parts of the sodium salt of aniline-Z-sulphonic acid, the pH of thereaction mixture being maintained between 7 and 8 by the addition ofsodium carbonate. The solution is then stirred for 2 hours, 30 parts ofpotassium chloride are added and the precipitated dyestuff is filteredoff. The filter cake so obtained is mixed with 1.03 parts of sodiumhydrogen phosphate and 1.97 parts of potassium dihydrogen phos phate anddried at 20 C.

When applied to cellulose textile materials in conjunction with atreatment with an acid-binding agent, with or without the application ofheat, bluish-red shades are obtained which are fast to Washing.

Example 8 A solution of 5.62 parts of sodium diethyldithiocar- 'bamatetrihydrate in 50 parts of water is added with stirring to a solution of17.9 parts of the trisodium salt of 7 (2 sulphophenylazo) 1 (4":6"dichloro 1":3": 5" triazin 2" ylamino) 8 naPhthol-BzG-disulphonic acid(which may be obtained as described in Example 1 of Britishspecification No. 785,222) in 400 parts of water and the resultingmixture is stirred for 3 hours at a temperature between 20 C. and 22 C.parts of sodium chloride are then added and the dyestulf which isprecipitated is filtered off. The filter cake so obtained is mixed with0.99 part of disodium hydrogen phosphate and 2.01 parts of potassiumdihydrogen phosphate and the mixture is dried at a temperature between20 and 25 C. On analysis the dyestulf is found to contain 5 sulphuratoms and 1 organically bound chlorine atom for each molecule ofdyestuff.

When applied to cellulose textile materials in conjunction with atreatment with an acid-binding agent the dyestuif yields red shadespossessing excellent fas'tness to washing.

The following table gives further examples of the new dyestuffs of theinvention which are obtained in the manner described in Examples 1 to 6by condensing the dithiocarbamic acid derivative listed in the thirdcolumn of the table with the dichlorotriazinylamino compound Whichis-i-tself obtained by condehsing cyanuric chloride with the aminoazocompound listed in the second column the i6 table with the. dichlorotriazinylarnino compound which is itself obtained by condensing cyanuricchloride With of the table. a the amlnoazo compound llsted '1n thesecond column of Example Aminoazo compound Dithiocarbamic acidderivative Shade on cellulose textile materialsl-amino-S-hydroxy-2:7-azonaphthalene-l13:6-trisulphonic acid Sodiumdiethyl dithiocarbamatd... .Bluish-red.

1-amino-7-[4'-(phenylazo)-2-methoxy-5-methyl-phcnylazo]-8- do Blue.

hydroxynaphthalene-3:2 :G-trlsulphonic acid.

1- (3-aminophenyl) -3'-carboxy-4-(1 :5"-disolphonaphthyl-2-azo)-5- J nYellowpyrazolone.

2-meihylamin0-5-hydroxy-6:2-az onaphthalene-7:1:5'-trisulphonic Sodiumdi-n-propyl-dlthiocarb amate. Orange.

aci Y r 1-(2:5-dich1orophenyl)-3-methyl-4-(8-aminopheny1azo)-5- Sodiumdicyelohexyl-dithiocarbamatc.. Yellow.

2-(4-amino-2-methylphcnylazo)naphthalene-4:8-disulphonic ae1d Sodiumdimethyl-dithiocarbamate. ;Do.

1-amin0-8:2-d.ihydroxy-7-(phenylazo)-naphthalene-3:5 :G-tri- Sodiumdiethyl-dithiocarbamate- Blue.

sulphonic acid.

l-amino-S:2-dihydroxy-7-(3-nitrophenylazo)naphthalene-3:526- 'Do.

disulphonie acid.

2-aruino-6-[2-methoxy-5-mcthyl-4-(2:5-disulphophenylazo) Bluish-violet.

phenylazol-E-naphthol-l:7-disulpl1onie acid.

1:2-cobalt complex of 1-(3-amino-4-sulph0pheuyl) 3-methyl-4-(2- Yellow.

carboxyphenylazo)-5-pyraz olone. V

l-berlizgylaminocii (3 -aminophenylazo) -8-naphthol-3:6:6-tn- Sodiumdrphenyl dithiocarbamate Red.

su p omc aci 1:2-chromium complex of2-amino-5-hydroxy-6-(2-carboxyphenyl- Sodium pcntamethylencdlthiocarbamate- Brown.

azo)naphthalene-7-sulphonic acid.

The following table gives further examples of the new 25 the table. Thefourth column of the table indicates the dyestuffs of the inventionwhich are obtained by the method described by Example 8 by condensingthe dithiocarbamic acid derivative listed in the third column of .shadesobtained when the dyestuffs are applied to cellu lose textile materialsin conjunction with a treatment with an acid-binding agent.

Shade obtained on Example Aminoazo compound Dithiocarbamie acidderivative cellulose telxtile ma eria s 211-amino-7-(2-sulphophenylazo)-8-naphthol-3:G-disulphonic acid Soiiumt N-methyl-N cyclohexyldithiocar- Red.

. r r ama e. 22 do Sodium N-ethyl N-benzyldithiocarbamate Do. 23 SodiutmN-methyl-N-phenyldithioearba- Do.

- ma e. 1-fimfino-7-(pheny1azo)-8naphthol-3:G-disulphonie acid Sodiumdiethyldithiocarbamate Do.2-(4'-amino-2'-methylphenylazo)-naphthalene-4z8-disulphonic acld. doYellow.. 2-amino-6-(2'-sulphophenylazo)-5-naphthol-7-sulphonic acidOrange.

2-amino-7-(2-su1ph0phenylazo)-8-naphtho1 6'sulph0nic acid Do. 1 (2:5dichloro-i sulphophenyl) 3 methyl 4 (3 amino-6" Yellow.

sulphophenylazo)-5-pyrazolone. 1 (2 chloro 5 sulphophenyl) 3 methyl 4(3" 2 amino -6- D0.

sulphophenylazo)-5-pyrazolone. 2 amino 6 (2 sulpho 4 methoxyphcnylazo) 5naphthol 7- Scarlet. V

sulphonic acid. 2 amino 7 (2 sulpho 4 methoxyphenylazo) 8 naphthol 6-Red.

sulphonic acid. 32 2 methylamino 7 (2 sulpho 4 mcthoxyphenylazo) 8 naph-D0.

thol-fi-sulphonic acid. 332-amino-5-hydroxy-6:2-azonaphthalene-7:1:5'-trisulphonic acid Orange. 342 methylamino 5 hydroxy 6:2 axonaphthalene 7:1'z5 trisul- Do.

phonic acid. 35'. 1:2-chromium complex of2-amino-6-(2-carboxy-phenylazo)-5naph- Brown.

thol-7-sulphom'c acid. 36 do Sodimn N:N-pentamethylene dithiocarba- Do.v

' mate. 7 37 do Sodium dimethyldithiocarbamate T Do. 38 do SodiumN-methyl-N-phenyldlthlocarba- Do.

mate. 4 gitro 4 ((i4 N methylaminophenylaz'o)stilbene 2:2 dlsul- Sodiumdiethyldithiocarbamate Reddrsh-yellow.

p omc aci 1;2-chromium complex ofG-amino-l:2-dihydroxy-6'-nitro-2:1-azo- Black-2amirio-8-hydroxy-7:2-azonaphthalenc-6:4:8-trisulphonic acidZ-amiuoS-hydroxyfl:2-azonaphthalenc-6:1:5-trisulphonic acid1-amino-7-(3-sulph0phenylazo)-8-naphthol-3zfi-disulphenic acid'2-(2-niethyl-4-aminophenylazo)naphthalene-5:7-disu1phonic aciddisulphonic acid. 1-(2'-sulphophenyl)-3-methyl-4-(3" -amino-6"-sulphophcnylazo)-5- pyrazolone. V

Reddlsh-orange. Orange.

Red.

Scarlet.

Do. Violet.

Reddish orange.

Red.

Do. Bluish-red.

Rubine.

Bluish-red. f

Red.

Rubine. Bluish-red.

Reddish-yellow.

V Brownish-orange.

Yellow.

' I Do. i

Shade obtained on Example Aminoazo compound Dithiocarbamic acidderivative cellulose textile materials 621-(4'-aminophenyl)-3methyl-4-(1 :5 -disuJphnaphthyl-2' azo)-5- Sodiumdiethyldithiocarbamate Yellow yrnzolone. 63 1-gamino-et-sulphophenyl)-3-rnethyl-4-(l"-sulphonaphtl1yl-2"- do Do.

azo)-5-pyrazolone. 1- (4':8'-disulphonaphth-2-yl)-3-methyl-4(3' amino-6"Do.

sulphophenylazo)-5-pyrazolone.l-(3-am.ino-6-sulphophenylazo)-2-naphthol-6-sulphomc acid dn Orange.1-(3-aminohsulphophenylazo)-2-naphthol-GzS-disulphomc acid do Do. 2-(3armno-o-sulphophenylazo)-l-naphthol-3 sulphonic acid Sodiumdlmethyldithiocarbamate Do.-

2-(3'umino-6- ulphophenylazo)-l:S-dihydroxynaphthalene-BzfidoBlu1sh-red.

disulphonic acid.1-(3'-amino-6-sulphophenylaz0)-2-amino-8-nephthol-6sulphomc Red.-

acid. 1-acetylamino7-(3-amino-6-sulphophenylazo)-8-naphth0l-3:6- fl Do.

disulphonic acid.1-acetylamin0-7-(3'-aminc-6'-sulphophenylazo)-S-naphthol-4:G- do Do.

disulphonic acid.l-benzoylamino-7-(3'-amino-d-sulphophenylazo)-8-naphthol-3:6- do Do.

disulphonic acid.2-propionylamino-6-(3-amino-6-sulphophenylazo)-5-naphthol-7- rlnYellowish-red.

sul honic acid. 2 benizoylaminod(3'-amino-6'-sulphophenylazo)-5-napl1thol-7- Potassiumdiethyldlthiocarbamatc Do.

sulphonic acid.2-amin0-7-(3-amino-6'-sulphophenylaz0)-8-naphthol-6-sulphomc -do Do.

acid. 1-(4-qmino-2-sulphophenylazo)-2-naphthol-8-sulphonic acid do Red.2-acetylamino-6-(4-amino-2-sulphophenylazo)-5-naphthol-7- Sodiumdi-n-propylditluocarbamate Yellowish-rcd.

sul honic acid. 7 2-aceEylamino-7- (4-amino-2'-sulphophenylazo)-8naphthol-fidn R d sulphonic acid.1-(4'-arnino-2-sulphophenylazo)-2aminodnaphthol-fi-sulphonic d0Blnish-red.

acid. Lacetylamirao-I-(4-a1n ino-2-sulpl1ophenylazo)-S-naphth0l-3:6-disuld0 Violet.

honic aci Liienzoylaminofl-(4-amino-2-sulphopl1enylazo)-8-napht-h0l 4:6--do Bordeaux.

disulphonic acid.l-(3-aminophenyl)-3-metl1yl-4(2:5"-disulphophenylazo)-5- do Yellow.

pyrazolone. 1-(3"aminobenzoylamino)-7- (2-sulphophenylazo)-8-naphthol3:6- do Red.

disulphonic acid. i-(4'-a.minosulphonaphthl-ylazo)-4-(8"1sulph0naphth-W-ylazo) do Reddish-brown.

naphthalene sulphonic acid. ll-amino-2-(4"-aminophenylazo)-7-(4"-sulphophenylazo)-8naphthol- .-doGreen.

3:6-disulphonic acid.1-(4-aminobenzoylamh1o)-7-(2-snlphophenylazo)-8-naphthol-3:G- Red.

disulphonic acid. 1-ami1107-(2-sulphophenylaz0)-8-naphthol-3zfi-disulphonic acid Sodium-morpholinoditlnocarbornate Do. an Sodium N-methyl-N-phenyldithiocarba-Do.

me e. 89 rln Sodium N:N-di-isobutyldithiocarhamate- Do. 90 1-0-7-(2'sulphophenylazo)-8-naphth0l-3:6-disulpl1onic acid SodiutmN:N-pcntamethylenedithioearba- Do,

ma e. 91 2amino-(H2'-methoxy-5-methyl-4-(2":5"-disulphophenylazo) Sodiumdiethyldithiocarbamat-e Bluish-violet.

phenylazo1-5-naphthold:7-disulphonic acid.

Example 92 In place of the 18 parts of the trisodium salt of the azocompound used in Example 1 there are used 14.5 parts of the disodiumsalt of 4- (4":6"-dichloro-1":3":5"- triazin 2"ylamino)2'-nitrodiphcnylaminc-3:4-disul phonic acid (which may beobtained by condensing cyanum'c chloride with4-amino-2-nitro-diphenyl-amine-3:4- disnlphonic acid).

The dyestufi so obtained when applied to cellulose textile materials inconjunction with a treatment with an acidbinding agent yields yellowshades possessing excellent fastness to wet treatments.

Example 93 A solution of 19.6 parts of the trisodium salt of l-amino- 4[4 (4":6"-dichloro-1":3":5"-triazin-2"-ylamino]anilinoanthraquinone-2z3:5-trisulphonic acid (which may be obtained asdescribed in Example 1 of British specification No. 781,930) in 400parts of water is stirred at 20 C. and a solution of 563 parts of sodiumdiethyldithiocarbamate trihydrate in 50 parts of water is added duringminutes. The mixture is stirred at C. until reaction is complete andsodium chloride is then added. The precipitated dyestutt is thenfiltered oil, Washed with brine solution and dried at 20 C.

On analysis the dyestulf so obtained is found to contain 1.1 atoms oforganically bound chlorine and 4.9 atoms of sulphur per molecule ofdyestufi. When applied to cellulose textile materials in conjunctionwith a treatment with an acid-binding agent the dyestuif yields blueshades possessing excellent fastness to wet treatmentsl Example 94 Inplace of the 19.6 parts of the trisodium salt used in Example 93 thereare used 17.0 parts of the disodium salt of 1amino-4-[3-(4":6"-dichloros-triazin-2"-yl) amino]anilinoanthraquinone-Z:4-disulph0nic acid (which may be obtained asdescribed in Example 2 of Belgian specification No. 556,092).

When applied to cellulose textile materials in conjunction with atreatment with an acid-binding agent the dyestutf so obtained yieldsreddish-blue shades possessing excellent fastness to wet treatments.

Example 95 Example 96 A solution of 10.1 parts of cyanuric chloride in40 parts of acetone is slowly added with stirring to a mixture of 16.8parts of 4'-amino-2-nitrodiphenylamine-4-sulphondimethylamide, 8.4 partsof sodium bicarbonate, 30 parts of water and 360 parts of acetone, thetemperature of the resulting mixture being maintained between 15 and 25C., and the pH of the mixture being maintained at 6.4 by the addition ofan 8% aqueous solution of sodium bicarbonate. The mixture is stirred for1 hour at the above temperature. solid is then washed with 100 parts ofacetone. The combined filtrates are cooled to a temperature of 5 C. and

a solution of 13.4 parts of sodium diethyldithiocarbamate trihydrate in50 parts of water is then slowly added, the

temperature of the mixture being maintained between 5 and C. and the pHof the mixture being maintained at 8 by the addition of an aqueoussolution of sodium carbonate. The mixture is then stirred for 1 hour andthe solution so obtained is poured into 3000 parts of water at atemperature of 1 C. The precipitated dyestufl is then filtered ofi,washed with water and dried.

On analysis the dyestuff so obtained is found'to contain latom oforganically bound chlorine and 3 atoms of sulphur per molecule ofdyestuff. V

When dispersed in aqueous medium the dyestulf colours wool and polyamidetextile materials in bright yellow" shades which possess excellentfastness to wet treatments.

Example 97 On analysis the dystufi' so obtained is found to contain 1' Hatom of organically bound chlorine and 2 atoms of sul- The mixture isfiltered and the residual acid-binding agent the dyestulf yields redshades'which possess excellent fastness to wet treatments. 7

I A similar dyestuif is obtained when the 1.5 parts of aniline usedinthe above example are replaced by 128 parts of sodium phenate.

Example 100 i q 7 n A mixture of 2.11ipa-rts'of4-aminoQ-methylazobenzene, 4.06 parts of2-chloro-4-(N:N-diethylthiooarbamylthio)-6-phenyl-1:3z5-triazine, 1.26parts of sodium bicarbonate and 100 parts of dioxan is stirred at theboil under a reflux condenser for 8 hours. The mixture is then added to200 parts of a 10% aqueous-solution of brine and'the dyestufi which isprecipitated is filtered 01T, washed 'with water and dried.

The dyestuii so obtained, when dispersed in aqueous medium, dyes wooland p olyarnide textile materials in 7 yellow shades which possessexcellent fastness towashing.

The 2-chloro-4- (N N-diethylthiocarb amylthio) -6-phenyl-1:3:5-triaz'ineused in the above example may be obtained as follows: i

A solution of 5.6 parts of sodium diethyldithiocarbamate trihydrate in100 parts of water is added over 1 hour with stirring'to a suspension of5.6 parts of 2:4-dichlo-ro- 6-phenyl-1 :3 S-triazine in a mixture ofparts ofgacetone and 200 part-sot water, the temperature of the mixturebeing maintained at 15 C. The mixture is then stir-red for -a further 45minutes at 15 C., and the precipitate is of chlorine and 1 8.9% ofsulphur.)

phur per molecule of dyestuff. When dispersed in aqueous medium thedyestufr colours polyamide textile materials in bright greenish-yellowshades of excellent fastness to light.

I Example 98 A mixture of 618 parts of sodium diethyldithiocar bamatetrihydrate, 3.4 parts of 1-arnino-4-[4-(4":6-die chloro 1" 3"5"-triazin-2-ylamino -anilino] anthraquinone and 165 parts of dioxan isstirred for 24 hours at a temperature of 25 C. The mixture is thenfiltered and the filtrate so obtained is added to 400 parts of a 10%aqeuous solution of sodium chloride. The dyestutf which is precipitatedis then filtered oil, Washed with water and dried.

On analysis the dyestufr so obtained is found to contain 0.9 atom oforganically bound chlorine and 2.1 atoms of sulphur per molecule ofdyestufi.

When dispersed in aqueous medium the dyestuif colours polyamide textilematerials in blue shades possessing excellent fastness to wettreatments.

Example 99 tween 7 and 8by thegradual addition of a 10% aqueous solutionof sodium carbonate. '12 parts of sodium chlo-" ride are then added andthe dyestufl which is precipitated in filtered 0E and dried.

.On analysis the dyestufi so obtained is found to contain 7 5 sulphuratoms, but'no atom of organically bound chlo-- rine per molecule ofdyestuff. When applied to cellulose textile materials in conjunctionwith a treatment with an then filtered off, washed with water and dried.After crystallisation from a light petroleum .ether (boiling point 60 toC.) the2-chloro-4-(N:N-diethylthiocarbamylthio)-6-phenyl-'113:5-triazine meltsat 67 to 68 C. On analysis the product is found .to contain 49.6% ofcarbon,

. 4.7% of hydrogen, 16.6% of nitrogen, 11.2% of chlorine (C14H15N4O1S2requires I and 17.7% of sulphur. of carbon, 4.45% of hydrogen, 16.6%ofnitrogen, 10.6%

7 Example 101 A mixture of 9.6 parts of the dyestufi of Example 15, 3parts of coppers-ulphate pentahydrate and 130 parts of water is stirredfor 4 hours at a temperature between 25 and 30 C., the pH of the mixturebeing maintained between 6.0 and 6.5 by the gradualaddition of anaqueous solution of sodium carbonate. An aqueous solution of sodiumcarbonate is then added until the pH of the mixture is-7 and the mixtureis filtered. 40 parts of sodium chloride are added to the filtrate whichis obtained and .the dyestuif which is precipitated is filtered off. The

filter-cake so obtained is mixed with 0.99 part of disodium hydrogenphosphate and 2.0 1 parts of potassium dihyd-rogen phosphate and themixture is then dried.

On analysis the dyestult so obtained is found to contain 1 atom ofcopper and 7 atoms of sulphur per molecule of dyestuif. When applied tocellulose. textile'materials in conjunction with a treatment with anacid-binding agent the dyestutr' yields violet shades possessingexcellent fastness to washing. V

In place of the 9.6 parts of the dyestutf of Example 15 used in theabove example there are used equivalent amounts of the dyestuiis ofExamples 16, 17 and 91 whereby c opperrcontaining dyestuffs are obtainedwhich .when applied to cellulose textile materials in conjunction with atreatment with an acid-binding agent'yield violet, navyblue and navyblueshades'respective'ly which possess ex cellent fastness to washing. V

v Example 102 I 7 d parts of bleachedcottonfabric are padded through anaqueous solution containing 2% of the dyestufl? of Example 1, 1% ofsodium bicarbonate and 0.2% of an alkylated phenol/ethylene oxidecondensate, at a temperature 21 ture of 102 C. for 1 minute. Thecoloured cotton fabric is then rinsed in water, immersed for 15 minutesin a 0.2% aqueous solution of soap, rinsed :again in water and finallydried.

The cotton fabric is thereby coloured a bright red shade possessingexcellent fastness to washing.

In place of the 2% of the dyestufi of Example 1 used in the aboveexample there is used 2% of the dyestufr of Example 2 or 2% of thedyestufi of Example 3 or 2% of the dyestuff of Example 5 or 2% of thedyestuff of Example 8 whereby the cotton fabric is coloured in brightyellow, bright blue, bright red and bright red shades respectively,which possess excellent tastness to washing.

Example 103 100 parts of bleached cotton yarn are immersed in a dyebathcomprising 2 parts of the dyestufi of Example 3 and 90 parts of sodiumchloride dissolved in 3000 parts of water and dyeing is carried out {or30 minutes at a temperature of 20 C. 15 parts of sodium carbonate arethen added and dyeing is continued for 60 minutes at 20 C. The dyedcotton yarn is then removed from the dyebath, rinsed in water, immersedfor 5 minutes in a 0.2% aqueous solution of a synthetic detergent at atemperature of 100 C., rinsed again in water and finally dried. Thecotton yarn is dyed a brilliant blue shade which is fast to washing.

In place of the 2 parts of the dyestutf of Example 3 used in the aboveexample there are used 2 parts of the dyestuff of Example 1, or 2 partsof the dyestufi of Example 33 or 2 parts of the dyestutf of Example 60whereby the cotton yarn is dyed in bright red, bright orange and brightyellow shades respectively, which possess excellent fastness to washing.

Example 104 100 parts of bleached cotton fiabric are padded through anaqueous solution containing 0.2% of the dyestufi of Example 1 and 2% ofsodium carbonate and the cotton fabric is then passed between rollersuntil its weight is 200 parts. The cotton fabric is then rolled up andstored for 4 hours at a temperature of 20 C. The cotton fabric is thenrinsed in water, immersed for 5 minutes in a 0.2% aqueous solution of asynthetic detergent at a temperature of 100 C., rinsed again in waterand dried. The cotton fabric is coloured a bright red shade possessingexcellent fastness to washing.

Example 105 100 parts of woollen cloth are immersed in a dyebathcomprising a solution of 1.5 parts of the dyestutf of Example 30, 3.0parts of ammonium acetate, 0.5 part of Water Sodium bicarbonate 1.5

A print paste comprising:

Parts The dyestufi of Example 92 3 Urea 4% aqueous solution of sodiumalginate 35 is applied to unmerceri'sed cotton cloth by machineprinting. The printed cotton cloth is dried at a temperature of C. andis then steamed for 6 minutes at a temperature of C. The printed cottoncloth is then rinsed in water, immersed for 10 minutes in a 0.3% aqueoussolution of a synthetic detergent at a temperature of 100 C., rinsedagain in water and finally dried.

The cotton cloth is thereby printed a brown shade which possessesexcellent fastness to Wet treatments.

In place of the unmercerised cotton cloth used in the above examplethere may be used mercerised sateen cloth or viscose rayon cloth whenbrown prints are also obtained which possess excellent fastness to wettreatments.

In place of the 3 parts of the dyestutf of Example 92 used in the aboveexample there are used 3 parts of the dyestutf of Example 1, or 3 partsof the dyestufi of Example 3 or 3 parts of the dyestufi of Example 24 or3 parts of the dyestuif of Example 93 or 3 parts of the second dyestuifof Example 99 whereby there are obtained red, blue, red, blue and redprints respectively which possess excellent fastness to washing.

The following table gives further examples of dyestuffs of the inventionwhich are obtained when the 1.5 parts of aniline used in Example 99 arereplaced by equivalent amounts of the compound listed in the secondcolumn of the table, and/ or the 8.3 parts of the dyestuff of Example 8used in Example 99 are replaced by equivalent amounts of the dyestuitslisted in the third column of the table. The fourth column of the tableindicates the shades obtained whenthe dyestuffs are applied to cellulosetextile materials in conjunction with a treat ment with an acid-bindingagent.

Example Compound Dyestufi Dimethyla do Do: B-Hydroxyethylamins do Do.

Di(fl-hydroxyethyl) amine Sodium sulphite..-

Oyclohexylamine do Do:

Mornh at i n a P iperidine- N igliethylaniline Sulphanilic avidm-Aminobenzoic acid. s-snlpho-N-methylaniline 5-sulpho-anthranilic acid.3:5-disulphoaniline 2:5-disulphoaniline Dyegtufi of Example 25--- Yggbw.o

Dyestinft of Example 30 Scarlet. Dyestufi of Example 35 do Dyegtufi ofExample 8- 3:5-disulpho-N-methylaniline 3-methy1amino-benzoie acid5-sulpho-2-methylaminobenzoic acid. Ammonium hydroxide Dyestufi ofExample 36- Brown.

23" Example .130

In place of the 17.9 parts of the trisodium salt of the azo compoundused in Example 8 there are used 19.9

parts of the trisodium salt of 7-(2'-sulphophenylazo)-1- (4":6"-dibromo-1":3":5"-triazin-2"-ylamino) 8 naphthol-3z6-disulphonic acid(which may be obtained as described in the example of Britishspecification 'No.

838,343) when a similar red dyestuif is obtained which, on analysis isfound to contain. sulphur atoms and one organically bound bromine atomper molecule of dyestutf.

7 Example 131 In place of the 4.06partsof.2-chloro-4-(NzN-diethylthiocarbarnylthio)-6-phenyl-123:5-triazineused in Example 100 there are used 6.16 parts of2-chloro-4-(NzN-diethylthiocarbamylthio) 6 (3:5'-disulphophenylamino)-,lz3z5-triazine or 3.5 parts of2-chloro-4-(NzN-diethylthiocarbamylthio)-6-meth0Xy-1:3:5-triazine or3.34 parts 2 4-dichloro-6-(3' 5-disulphophenylamino)-l :3 S-triazine, 24-diChloro-6-methoxy-1 :3 S-triazine,

2 4-dichloro-6-amino-1 :3 :S-triazine,

2: 4-dichloro-6-(N-m-sulphophenyl-N methylamine)-1 :3

' S-triazine or 2:4-dichloro'-6'-.methyl-1 :3 :S triaZine respectively;

Example132 1 A solution of 3.0 parts of sodium dimethyldithiocarbamatein 15 parts of Wateris added to a solution of 3.0 parts of the disodiumsalt of 1-(4': 6'-dichloro-1':3:5'-. triazin-2'-amino)-7-phenylazo-*8-naphthol-3 :6 disulphonic acid (which is obtainedas'described in Example 1 of United States patent specification No.1,667,312) in 7 0 parts of Water, and'the resulting mixture is stirredfor 16 hours at 20 C. The mixture is then filtered and 18 parts ofsodium chloride are added to the resulting filtrate. The dyestutf whichis precipitated is then filtered Off, washed with a 20% aqueous solutionof sodium chloride and dried.

On analysis the dyestuff is found to contain 6 sulfur atoms permolecular of dyestuif. When applied to cellulose textile materialsin'conjunction with a treatment with an acidabinding agent the dyestuifyields red shade-s possessing excellent fastness to light and to wettreatments. The dyestuff also-possesses excellent stability to storage'and this is superior to the stability to storage oft-he first dyestuifof Example 1 of United States patent specifica? tion No. 1,667,312. 7 7

What we claim is; J1. Dyestuffs of the formula:

wherein H K represent-s the radical of a dyestufi? selected from theclass consisting of azo, anthraquinone, nitro and phthalocyaninedyestufi radicals; V i

R represents a member'selected from the class consisting of hydrogen andlower alkyl;

n is a positive integer not exceeding 2;

.24 r Q is a member selected from the class consisting of chlorine,bromine, lower alkyl; phenyl, lower alkoxy,

sulponic acid, phenoxy, amino, lower alkylamino, hy-

:droxy lower alkylamino, phenylamino; sulphophenylamino,canboxyphenylamino; N-phenyLN-lower alkylarnino, N-sulphophenyl-N-loweralkylamino, lcanboxy-sulphophenylamino, N-(canboxysulphophenyl)-N-lo\veralkylamino, N-carboxyphenyl-N-lower alkylamino, disulphophenylamino,N-disulphophenyl- Nlower a lkylamino, cyclohexylamino, morpholino,piperidyl and I e a and Z and Z" are independently selected from theclass consisting of lower alkyl, phenyl lower alkyl, cyclohexyl andphenyl, and taken together Z and .Z" tfOIlTl with the nitrogen atom N aheterocyclic ring selected from the class consisting of piperidyl andmorpholino. V i

2. Dyestufi's of the formula:

' cs-iirNzz wherein K is an azo dyestufi radical, and Z is alowerwherein K is an lanthraquinone dyestuff radical, and Z is a lower alkylradical.

4. Dyestufis of the formula:

wherein K is a phthalocyanine dyestuff radical, and Z is a lower alkylradical.

5. Dyestuifs of the tformula:

-wherein K is an azo dyestuflf radical, and Z is a lower alkyl radical.

- 6 Dyestuffs of the formula:

wherein K is an anthraquinone dyestufi radical, and Z is.

a lower alkyl radical.

8. The 'dyestufi which, in the form of free acid, is of the formula 9.The dyestuff which, in the form of free acid, is of the formulaReferences Cited by the Examiner UNITED STATES PATENTS 4/ 28 Fritzscheet a1 260-153 -1 1/ 36 Orthner et a1 260249.5 6/59 Alsberg et a1.260.153 4/61 Andrew et a1. 260- 15 3 FOREIGN PATENTS 2/ 59 Belgium.

CHARLES B, PARKER, Primary Examiner.

1. DYESTUFFS OF THE FORMULA: